CN107068947B - Modified diaphragm for lithium-sulfur battery and preparation method thereof - Google Patents

Modified diaphragm for lithium-sulfur battery and preparation method thereof Download PDF

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CN107068947B
CN107068947B CN201710277216.6A CN201710277216A CN107068947B CN 107068947 B CN107068947 B CN 107068947B CN 201710277216 A CN201710277216 A CN 201710277216A CN 107068947 B CN107068947 B CN 107068947B
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lithium
mil
diaphragm
sulfur
modified diaphragm
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CN107068947A (en
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李忠涛
苏鑫
邓深圳
吴明铂
吴文婷
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China University of Petroleum East China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a modified diaphragm for a lithium-sulfur battery and a preparation method thereof, wherein the modified diaphragm is prepared by uniformly mixing a carbonized MIL-101 series metal organic framework material and a binder and coating the mixture on the surface of the diaphragm, wherein metal cations have strong adsorption effect on polysulfide, so that the polysulfide is prevented from being dissolved and the shuttle effect is limited and inhibited. The carbonized porous skeleton structure has good lithium ion conductivity, plays a role of a current collector and is beneficial to the rapid conduction of electrons. The modified diaphragm shows excellent cycle performance and rate performance when used for a lithium-sulfur battery. And the preparation method is simple, low in cost, environment-friendly and has good industrial application prospect.

Description

Modified diaphragm for lithium-sulfur battery and preparation method thereof
Technical Field
The invention relates to the field of chemical power sources, in particular to a modified diaphragm for a lithium-sulfur battery and a preparation method thereof.
Background
The rapid rise of modern electric automobiles puts higher and higher requirements on the energy density of batteries, the lithium ion batteries which are commercially used at present cannot meet the application requirements of some electronic equipment, and the lithium sulfur batteries which are researched and heated in recent years have high energy density, and the theoretical energy density of the lithium sulfur batteries reaches 2600Wh & kg-1The lithium battery is 5 times of a commercial lithium battery, meets the requirements of electric automobiles on batteries, and also meets the requirements of electronic portable equipment on lightness, smallness and thinness of the batteries.
The lithium-sulfur battery is a secondary high-density energy battery system which is constructed by taking metal lithium as a negative electrode and taking elemental sulfur or a sulfur-based composite material as a positive electrode. The theoretical specific capacity of elemental sulfur can reach 1675 mAh.g-1In addition, the elemental sulfur has the characteristics of low cost, abundant resources, environmental friendliness and the like, so that the elemental sulfur is widely applied to lithium secondary batteries.
Despite the advantages of lithium sulfur batteries, many challenges and difficulties remain, such as the insulation of elemental sulfur and the redox product lithium sulfide, the dissolution of polysulfide ions, andits "shuttle effect", stability problems of the lithium metal negative electrode, etc. Most seriously, polysulfide anion formed in the process of charging and discharging is easy to dissolve and diffuse in the organic electrolyte, and generates an insulating precipitate (Li) by side reaction with the positive electrode sulfur material and the negative electrode lithium plate2S2And Li2S), the process reduces the coulomb ratio of the lithium-sulfur battery on one hand, and also causes the loss of active substances on the other hand, so that the capacity of the lithium-sulfur battery is rapidly attenuated, and the utilization rate of the active substances is greatly reduced. The successful suppression of the shuttling effect of the intermediate polysulfide becomes the key to the preparation of high-performance lithium sulfur batteries. If the structural characteristics of the lithium-sulfur battery can be utilized, a diaphragm capable of effectively blocking shuttle of polysulfide is designed, and the capacity performance and the cycle performance of the lithium-sulfur battery can be greatly improved.
To prevent the shuttling effect of polysulfides, the academia has been studied in recent years mainly from several aspects: (1) preparing a porous carbon material to coat sulfur to form a carbon-sulfur composite material, and dispersing elemental sulfur in the porous carbon material to inhibit the dissolution of polysulfide in electrolyte; (2) adding some additives to the electrolyte to optimize the composition of the electrolyte or to use a new electrolyte; (3) modifying and protecting the metal lithium cathode, and organizing the corrosion of electrolyte and polysulfide to the lithium cathode; (4) the barrier layer is designed to block the dissolution of polysulfides.
Based on the research, the invention takes the lithium-sulfur battery diaphragm as a research object, and improves the capacity performance and the cycle performance of the lithium-sulfur battery by modifying a layer of carbonized MIL-101 series metal organic framework material on the surface of the commercial battery diaphragm. Wherein the metal cation has strong adsorption effect on polysulfide, prevents polysulfide from dissolving, and has limited shuttle inhibition effect. The carbonized porous skeleton structure has good lithium ion conductivity, plays a role of a current collector and is beneficial to the rapid conduction of electrons. The modified diaphragm shows excellent cycle performance and rate performance when used for a lithium-sulfur battery. And the preparation method is simple, low in cost, environment-friendly and has good industrial application prospect.
Disclosure of Invention
Aiming at the existing defects of the lithium-sulfur battery, the invention aims to provide a modified diaphragm for the lithium-sulfur battery, which can effectively inhibit polysulfide shuttling, and a preparation method thereof, so as to improve the specific capacity and the cycling stability of the lithium-sulfur battery; and the preparation method is simple to operate, low in cost and suitable for industrial production.
The invention is realized by the following technical scheme:
a modified diaphragm for a lithium-sulfur battery and a preparation method thereof are disclosed, wherein the modified diaphragm is prepared by uniformly mixing an MIL-101 series metal organic framework material subjected to carbonization with a binder and then coating the mixture on a diaphragm; the preparation process comprises the following steps: calcining the MIL-101 series metal organic framework material to obtain a carbonized active material; adding N-methyl pyrrolidone into the carbonized active material and the binder according to the mass ratio of 7:0-7:3, and uniformly mixing to obtain coating slurry; and uniformly coating the slurry on the surface of the diaphragm, and drying in vacuum to obtain the modified diaphragm.
On the basis of the scheme, the MIL-101 series metal-organic framework material is one or more of NH2-MIL-101(Al), NH2-MIL-101(Fe), NH2-MIL-101(Cr) and MIL-101 (Cr).
On the basis of the scheme, the carbonization temperature is 600-1100 ℃ for the modified diaphragm for the lithium-sulfur battery and the preparation method thereof.
On the basis of the scheme, the modified diaphragm for the lithium-sulfur battery and the preparation method thereof are characterized in that the diaphragm is any one of a polyethylene diaphragm or a polypropylene diaphragm.
On the basis of the scheme, the calcination is carried out in an inert gas atmosphere.
On the basis of the scheme, the drying temperature is 40-100 ℃ for the modified diaphragm for the lithium-sulfur battery and the preparation method thereof.
On the basis of the scheme, the modified diaphragm for the lithium-sulfur battery and the preparation method thereof are characterized in that the positive electrode of the lithium-sulfur battery consists of sulfur and carbon black; the preparation process comprises the following steps: mixing and ball-milling sulfur and carbon black according to a mass ratio of 7:3, placing the sulfur/carbon black in a tube furnace under an inert atmosphere at 155 ℃ for 12 hours, and mixing the sulfur/carbon black composite material and a binder according to a mass ratio of 9:1, adding N-methyl pyrrolidone and uniformly mixing to obtain coating slurry; and uniformly coating the slurry on the surface of an aluminum foil, and drying in vacuum to obtain the lithium-sulfur battery anode.
The effective gains of the present invention are:
according to the invention, the carbonized MIL-101 series metal organic framework material is coated on the surface of the diaphragm, and when the modified diaphragm is used for a lithium-sulfur battery, the electrochemical performance of the modified diaphragm is greatly improved. Wherein the metal cation has strong adsorption effect on polysulfide, prevents polysulfide from dissolving, and has limited shuttle inhibition effect. The carbonized porous skeleton structure has good lithium ion conductivity, plays a role of a current collector and is beneficial to the rapid conduction of electrons. The coating can still show good conductivity without adding any conductive agent.
Drawings
The invention has the following drawings:
FIG. 1 is NH2MIL-101(Al) and NH2SEM photograph of-MIL-101 (Al) -900, in which the photographs (a) and (b) are NH2SEM pictures of-MIL-101 (Al), in which (c) and (d) are NH2SEM picture of MIL-101(Al) -900;
FIG. 2 is NH2MIL-101(Al) and NH2TEM image of MIL-101(Al) -900, where image (a) is NH2TEM image of MIL-101(Al), FIG (b) NH2TEM image of MIL-101(Al) -900;
fig. 3 is a graph of capacity voltage and cyclic voltammograms of lithium-sulfur cells made in examples 1 and 3, wherein (a) is a graph of capacity voltage at 0.1C magnification followed by 0.5C magnification for the first two cycles of the lithium-sulfur cell made in example 1, (b) is a graph of capacity voltage at 0.1C magnification followed by 0.5C magnification for the first two cycles of the lithium-sulfur cell made in example 3, (C) is a graph of cyclic voltammogram of the lithium-sulfur cell made in example 1 at a scan rate of 0.1mV, and (d) is a graph of cyclic voltammogram of the lithium-sulfur cell made in example 3 at a scan rate of 0.1 mV.
FIG. 4 shows an embodimentLithium sulfur batteries made in examples 1, 2 and 3 were cycled at 0.1C rate twice before, and then 0.5C (1C 1675mAh g)-1) A circulation stability performance graph and a coulombic efficiency graph under multiplying power;
FIG. 5 is a graph showing the AC impedance of the lithium sulfur batteries manufactured in examples 1, 2 and 3;
fig. 6 is a graph of rate performance of lithium sulfur batteries manufactured in examples 1, 2 and 3.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
(1) Reacting NH2MIL-101(Al) was placed in a tube furnace and heated to 900 ℃ at 10 ℃/min under nitrogen protection for 5 hours. Obtaining NH carbonized at 900 DEG C2MIL-101(Al), marked NH2-MIL-101(Al)-900。
(2)NH2MIL-101(Al) -900 and PVDF are mixed uniformly according to a ratio of 9:1 and N-methyl pyrrolidone is added to obtain coating slurry; uniformly coating the slurry on the surface of a Celgard2400 diaphragm, and vacuum-drying at 60 ℃ for 12 hours to obtain a modified diaphragm marked as NH2-MIL-101(Al) -900 modified membranes.
(3) Mixing and ball-milling sulfur and carbon black according to a mass ratio of 7:3, placing the ball-milled sulfur/carbon black in a tubular furnace under a nitrogen atmosphere at 155 ℃ for 12 hours, and mixing the sulfur/carbon black composite material and a binder according to a mass ratio of 9:1, adding N-methyl pyrrolidone and uniformly mixing to obtain coating slurry; and (3) uniformly coating the slurry on the surface of the aluminum foil, and drying in vacuum at 60 ℃ to obtain the lithium-sulfur battery anode.
(4) And cutting the positive electrode material into sheets with the diameter of 12mm to prepare the pole pieces. Using metal lithium as a counter electrode, manufacturing a CR2032 button battery in a glove box filled with argon, and adopting NH as a diaphragm2-MIL-101(Al) -900 modified diaphragm with l.0 mol.L electrolyte-1The lithium bis (trifluoromethanesulfonyl) imide is dissolved in a mixed solution prepared from 1, 3-dioxolane and glycol dimethyl ether in a volume ratio of 1:1, and the additive is anhydrous lithium nitrate with the mass fraction of 1 wt%. The LandCT2001A battery test system is adopted to test the charge and discharge performance and the charge and discharge termination voltage of the sampleIs 1.7-3.0V. The cyclic voltammetry test adopts the electrochemical workstation of Shanghai Chenghua CHI760E to test, and the scanning rate is 0.1 mV.s-1And the voltage range is 1.5-3.0V.
Example 2
NH in (2) of example 12-MIL-101(Al) -900 changed to NH2MIL-101(Al), NH in step (4) of example 12-MIL-101(Al) -900 modified diaphragm into NH2MIL-101(Al) modified separator, the other is the same as in example 1.
Example 3
NH in the step (4) of example 12-MIL-101(Al) -900 modified membrane to original membrane, the other was the same as in example 1.
Results and analysis
NH can be seen from FIGS. 1(a), (b)2The shape of-MIL-101 (Al) is spherical and regular, and NH after carbonization at 900 ℃ is shown in figures 1(c) and (d)2The appearance of-MIL-101 (Al) -900 is basically kept unchanged, which shows that the skeleton structure of the material after high-temperature carbonization is kept good.
To further illustrate the morphology of the material, the material was subjected to TEM testing, as shown in FIG. 2, to further demonstrate NH2The material has a MIL-101(Al) spherical structure, the shape of the material is basically unchanged after high-temperature carbonization, and the internal pore structure is increased, so that the rapid transmission of lithium ions is facilitated.
FIG. 3 is a graph of capacity voltage and cyclic voltammograms of examples 1 and 3, as can be seen from FIGS. 3(a), (b), using NH2-MIL-101(Al) -900 modified separator Δ E between charge and discharge plateaus of lithium sulfur batteries prepared with 240mV, and Δ E between charge and discharge plateaus of lithium sulfur batteries prepared with the original separator 480 mV. Description of NH2The lithium-sulfur battery prepared by the-MIL-101 (Al) -900 modified diaphragm has lower electrode polarizability, smaller kinetic reaction barrier and higher reversibility. FIGS. 3(c) and (d) both show two distinct reduction peaks and one oxidation peak, with the higher reduction peak corresponding to the conversion of elemental sulfur to soluble lithium polysulfide (LiS) during dischargexX is more than or equal to 4 and less than or equal to 8), the lower reduction peak corresponds to the conversion of soluble lithium polysulphide into insoluble Li during the discharge process2S2And Li2S process, one oxidation peak corresponding to Li in the charging process2S2/Li2Conversion of S to S8The process of (1). This is consistent with the charge and discharge plateaus in the capacity-voltage diagrams of fig. 3(a), (b).
FIG. 4 is a graph of the cycling performance and coulombic efficiency for examples 1, 2 and 3, NH, after 90 cycles2-MIL-101(Al) -900 modified diaphragm cell, NH2The discharge specific capacities of the-MIL-101 (Al) modified diaphragm battery and the original diaphragm battery are 906.8mA g-1，359.6mAh·g-1，422.3mAh·g-1. NH can be seen2MIL-101(Al) -900 modified diaphragm batteries exhibiting high specific capacity and cycling stability, while NH2The MIL-101(Al) modified diaphragm battery has serious discharge specific capacity attenuation, and the original diaphragm has lower discharge specific capacity all the time. In addition, NH after 90 cycles2The coulombic efficiency of the-MIL-101 (Al) -900 modified diaphragm is still as high as 97.5%, while NH2Coulombic efficiencies of 84.5% and 90.4% for the MIL-101(Al) modified separator and the original separator cell, respectively, indicating NH2The MIL-101(Al) -900 modified diaphragm has good shuttle inhibition effect and the capability of improving the circulation stability.
For further analysis of NH2The reason why the MIL-101(Al) -900 modified diaphragm battery has good performance is that alternating current impedance tests are respectively carried out on the lithium-sulfur batteries with three different diaphragms. As can be seen from fig. 5, the ac impedance curve is composed of a circular arc in the high frequency region and a straight line in the low frequency region. The smaller the semi-circle diameter of the high frequency region, the smaller the resistance. NH in comparison to the original separator2The impedance of the-MIL-101 (Al) -900 modified diaphragm battery is greatly reduced, which shows that NH after carbonization2MIL-101(Al) has good conductivity, and when used for modifying a separator, the MIL-101(Al) does not affect the transmission of lithium ions, can also play a role of a current collector and improves the electron transmission speed. In addition, NH compares to the original membrane2Increased impedance of MIL-101(Al) modified separator cells, indicating non-carbonized NH2MIL-101(Al) is comparatively poor in conductivity.
To further illustrate NH2-MIL-101(Al) -900 modification of the good electrochemical performance of the diaphragm battery, and the rate capability test is carried out on the diaphragm battery. FIG. 6 is a graph showing the rate performance of a battery assembled with three separators, in which NH is shown2The specific capacities of the-MIL-101 (Al) -900 modified diaphragm battery at 0.5C, 1C, 2C, 4C and 8C can be respectively maintained at 1291.4 mAh.g-1、1065.8mAh·g-1、881.3mAh·g-1、741.1mAh·g-1、590.7mAh·g-1When the specific capacity is returned to 0.5C, the specific capacity can still be returned to 1084.2mAh g-1Description of NH2the-MIL-101 (Al) -900 modified diaphragm battery has good rate performance.
From the above analysis, it can be seen that NH2The MIL-101(Al) -900 modified diaphragm can prevent lithium polysulfide from diffusing to a negative electrode on the premise of not influencing lithium ion transmission, so that the shuttle effect of the lithium-sulfur battery is inhibited, and carbonized NH is generated2the-MIL-101 (Al) has good conductivity, can improve electron transfer, and can improve the conductivity of a positive electrode material. The lithium sulfur prepared by the lithium sulfur has higher specific capacity and coulombic efficiency, and good cycling stability and rate capability. The experiment opens up a new path for the development of the high-performance lithium-sulfur battery, and the method is simple, convenient, low in cost, environment-friendly and has good industrial application prospect.

Claims (1)

1. A modified diaphragm for a lithium-sulfur battery and a preparation method thereof are characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
reacting NH2Putting MIL-101(Al) into a tube furnace, heating to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen, and keeping for 5 hours to obtain NH carbonized at 900 DEG C2-MIL-101（Al）-900；
Reacting the NH with2MIL-101(Al) -900 with PVDF in a ratio of 9:1, adding N-methyl pyrrolidone, uniformly mixing to obtain coating slurry, uniformly coating the coating slurry on the surface of a Celgard2400 diaphragm, and performing vacuum drying at 60 ℃ for 12 hours to obtain NH2-MIL-101(Al) -900 modified diaphragm;
mixing sulfur and carbon black according to a mass ratio of 7:3, mixing and ball-milling, placing the mixture in a tube furnace under the nitrogen atmosphere at 155 ℃ for 12 hours, and mixing the mixture with a binder according to the mass ratio of 9:1, adding N-methyl pyrrolidone, uniformly mixing, uniformly coating on the surface of an aluminum foil, and performing vacuum drying at 60 ℃ to obtain a lithium-sulfur battery positive electrode material;
cutting the anode material into sheets with the diameter of 12mm to prepare pole pieces, taking metal lithium as a counter electrode, and preparing a CR2032 type button battery in a glove box filled with argon, wherein a diaphragm adopts NH2-MIL-101(Al) -900 modified diaphragm with l.0 mol.L electrolyte -1The lithium bis (trifluoromethanesulfonyl) imide is dissolved in a mixed solution prepared from 1, 3-dioxolane and glycol dimethyl ether in a volume ratio of 1:1, and the additive is anhydrous lithium nitrate with the mass fraction of 1 wt%.
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